The effects of substitution on tetrakis­(substituted imidazole)­copper(II) tri­fluoro­methane­sulfonates

The organic ligands 4-methyl-1H-imidazole and 2-ethyl-4-methyl-1H-imidazole react with Cu(CF₃SO₃)₂·6H₂O to give tetrakis(5-methyl-1H-imidazole-κN³)­cop­per(II) bis­(tri­fluoro­methane­sulfonate), [Cu(C₄H₆N₂)₄](CF₃SO₃)₂, and aqua­tetrakis(2-ethyl-5-methyl-1H-imidazole-κN³)copper(II) bis(tri­ fluoro­methane­sulfonate), [Cu(C₆H₁₀N₂)₄(H₂O)](CF₃SO₃)₂. In the former, the Cu atom has an elongated octahedral coordination environment, with four imidazole rings in equatorial positions and two tri­fluoro­methane­sulfonate ions in axial positions. This conformation is similar to those in the analogous complexes tetrakis­(imidazole)­cop­per(II) tri­fluoro­methane­sulfonate and tetrakis(2-methyl-1H-imidazole)­cop­per(II) tri­fluoro­methane­sulfonate. In the second of the title compounds, the ethyl groups block the central Cu atom, and a square-pyramidal coordination environment is formed around the Cu atom, with the substituted imidazole rings in the basal positions and a water mol­ecule in the axial position.

S1. Comment

It is important to synthesize simple Cu^II–imidazole complexes and study their structures in order to help us understand the interactions of histidyl residues with copper ions in metalloproteins (Jian et al., 1999; Wang et al., 1999; Ohtsu et al., 2001). For example, the counter-ion effects on the structures of copper complexes have been revealed by structural studies and comparisions of nitrate (McFadden et al., 1976), sulfate (Fransson & Lundgerg, 1972), perchlorate (Ivarsson, 1973) and trifluoromethanesulfonate (Liu & Su, 1995) complexes of tetrakis(imidazole)copper(II). Similarly, the substituting effects of imidazole on their complexes can be investigated by structural studies of the corresponding complexes?. The crystal structures of tetrakis(imidazole)copper(II) trifluoromethylsulfonate, (I) (Liu & Su, 1995), and tetrakis(2-methylimidazole)copper(II) trifluoromethanesulfonate, (II) (Liu et al., 2002), have been reported previously. We report here the preparation and X-ray crystal structure determination of another two analogous complexes, viz. tetrakis(5-methyl-1H-imidazole-κN³)copper(II) trifluoromethanesulfonate, (III), and tetrakis(2-ethyl-5-methyl-1H-imidazole-κN³)copper(II) trifluoromethanesulfonate, (IV).

The crystal structure of (III) (Fig. 1) consists of discrete molecules. The structure of (III) is similar to the structures of (I) and (II). The coordination environment of the central Cu ion can be described as an elongated? octahedron with four N atoms of the substituted imidazole rings at the equatorial positions and two O atoms from the trifluoromethylsulfonate groups at the axial positions. The lengths of the Cu—N bonds are in the usual range [1.992 (4)–2.001 (4) Å], while the lengths of the axial Cu—O bonds [2.639 (3) and 2.867 (4) Å] are significantly longer than those found in (I) (2.593 Å; Liu & Su, 1995) and shorter than those found in (II) (2.651 and 3.069 Å; Liu et al., 2002). However, in the (IV), the larger substituent, i.e. the ethyl group, at the 2-position of the imidazole ring blocks the central Cu atom and allows the coordination environment around the Cu atom to become square pyramidal, with four N atoms of substituted imidazole rings at basal positions and a water molecule at the axial position, as shown in Fig. 2. The Cu—N bonds have typical lengths [1.997 (5)–2.026 (6) Å] and the axial Cu—O bond is 2.373 (5) Å, which is significantly shorter than those found in the hexacoordinated copper complexes (I), (II) and (III). The closest-contact distance between the Cu atom and an O atom of a trifluoromethanesulfonate group is longer than 4 Å, which suggests that the anion groups are free counter-ions in the crystal structure of (IV). Figs. 3 and 4 show the crystal packing of (III) and (IV), respectively. The complexe cations and trifluoromethylsulfonate ions are connected by possible hydrogen-bonding interactions, which were denoted by dashed lines in Figs. 3 and 4.

It was found that the conformations of the organic ligands in (I)–(IV) are affected by the substituents on the imidazole ring and the substituted positions. The dihedral angles between the imidazole planes and the CuN₄ plane of the coordination polyhedron are listed in Table 2.

In (I), which contains unsubstituted imidazole rings, two imidazole rings are almost perpendicular to the equatorial plane and the other two are tilted by 59.4°. All imidazole rings with a substituent at the 2-position in (II) and (IV) are tilted by 47.2–61.3° with respect to the CuN₄ plane of the coordination polyhedron. However, one of the imidazole rings with a substituent at the 4-position is almost parallel to the equatorial plane, and the other three lie nearly perpendicular to it in (III).

We conclude that the substituents and their positions on the imidazole ring can affect the structure of copper–imidazole complexes, specifically the coordination number of the Cu ion, the bond lengths of axial Cu—O bonds and the dihedral angles between the plane of the imidazole ring and the CuN₄ plane of the coordination polyhedron. However, there is almost no influence on the Cu—N bond lengths.

S2. Experimental

The organic ligands 4-methyl-1H-imidazole and 2-ethyl-4-methyl-1H-imidazole (Merck), 2,2'-dimethoxypropane (Aldrich), cupric oxide (Merck), trifluoromethylsulfonic acid (Aldrich), and organic solvents of reagent grade were used as received. Cu(CF₃SO₃)₂·6H₂O was prepared from CuO and CF₃SO₃H. The title compounds were prepared by the following procedure: Cu(CF₃SO₃)₂·6H₂O (1 mmol) and the corresponding ligand (4 mmol) were dissolved in acetonitrile containing 5% 2,2-dimethoxypropane. The mixture was stirred at room temperature for 2 h, and then diethyl ether was added dropwise until a precipitate began to appear. The solution was stored in a refrigerator for 2 d and yielded dark-blue crystal [yield 92 and 65% for (III) and (IV), respectively].

S3. Refinement

All H atoms were positioned geometrically and were treated as riding on their parent atoms in the final refinement. The ethyl group in (IV) is diorientationally disordered and was represented by atom C4/C5 and C4/C5'. The occupancies of atoms C5 and C5' were fixed at 0.55 and 0.45, respectively, in the final refinement, according to the results of occupancy refinement.

Computing details

Data collection: CAD-4-PC (Enraf-Nonius, 1992) for (III); CAD-4-PC (Enraf–Nonius, 1992) for (IV). For both compounds, cell refinement: CAD-4-PC; data reduction: XCAD4/PC (Harms, 1997); program(s) used to solve structure: SHELXTL (Bruker, 1997). Program(s) used to refine structure: SHELXTL) for (III); SHELXTL for (IV). For both compounds, molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The molecular structure of (III), showing displacement ellipsoids at the 35% probability level and the atomic numbering scheme.
	Fig. 2. The molecular structure of (IV), showing displacement ellipsoids at the 35% probability level and the atomic numbering scheme.
	Fig. 3. The crystal packing of (III), viewed along the b direction. Crosshatched circles denote Cu and S atoms, circles shaded by slanting lines denote F and O atoms, open circles denote N atoms, and circles shaded by dots denote C atoms. Hydrogen bonds are denoted by dashed lines.
	Fig. 4. The crystal packing of (IV), viewed along the b direction; atoms are represented as described in Fig. 3. Hydrogen bonds are denoted by dashed lines.

(III) tetrakis(5-methyl-1H-imidazole-κN³)copper(II) trifluoromethanesulfonate

Crystal data

[Cu(C4H6N2)4](CF3SO3)2	F(000) = 1404
Mr = 690.11	Dx = 1.622 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 16.400 (3) Å	θ = 10.3–15.0°
b = 10.174 (2) Å	µ = 1.01 mm^−1
c = 17.016 (3) Å	T = 293 K
β = 95.50 (3)°	Prism, blue
V = 2826.1 (9) Å^3	0.4 × 0.3 × 0.2 mm
Z = 4

Data collection

Enraf–Nonius CAD-4 diffractometer	2890 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.025
Graphite monochromator	θmax = 25.0°, θmin = 2.3°
ω scan	h = −19→19
Absorption correction: ψ scan (North et al., 1968)	k = 0→12
Tmin = 0.706, Tmax = 0.817	l = 0→20
5140 measured reflections	3 standard reflections every 7200 min
4954 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.103	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.001P)^2 + 7P] where P = (Fo^2 + 2Fc^2)/3
4954 reflections	(Δ/σ)max = 0.006
370 parameters	Δρmax = 0.36 e Å^−3
36 restraints	Δρmin = −0.31 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cu1	0.22066 (4)	0.22516 (6)	0.15852 (3)	0.04250 (16)
S1	0.12378 (8)	−0.05689 (12)	0.01003 (7)	0.0441 (3)
S2	0.34659 (8)	0.53309 (13)	0.26798 (8)	0.0512 (3)
F1	0.2757 (3)	−0.1386 (5)	0.0277 (3)	0.1318 (19)
F2	0.2496 (2)	0.0009 (5)	−0.0651 (3)	0.1059 (14)
F3	0.2108 (2)	−0.1983 (4)	−0.0796 (2)	0.0950 (12)
F4	0.4582 (3)	0.6563 (5)	0.1991 (2)	0.142 (2)
F5	0.3920 (3)	0.5142 (5)	0.1257 (2)	0.1315 (19)
F6	0.4816 (3)	0.4559 (7)	0.2167 (3)	0.159 (2)
O1	0.1471 (2)	0.0404 (4)	0.0688 (2)	0.0609 (10)
O2	0.0761 (2)	−0.0098 (4)	−0.0590 (2)	0.0673 (11)
O3	0.0968 (3)	−0.1784 (3)	0.0409 (2)	0.0772 (13)
O4	0.3153 (2)	0.4033 (4)	0.2611 (3)	0.0755 (12)
O5	0.2870 (3)	0.6289 (4)	0.2411 (3)	0.0959 (16)
O6	0.3906 (2)	0.5710 (5)	0.3398 (2)	0.0961 (17)
N1	0.1252 (2)	0.2628 (4)	0.2190 (2)	0.0427 (10)
N2	0.0469 (3)	0.3349 (4)	0.3060 (2)	0.0573 (12)
H2A	0.0305	0.3773	0.3481	0.069*
N3	0.2577 (2)	0.0872 (4)	0.2378 (2)	0.0428 (10)
N4	0.2950 (3)	−0.1030 (4)	0.2876 (2)	0.0547 (12)
H4A	0.3041	−0.1901	0.2917	0.066*
N5	0.3246 (2)	0.2032 (4)	0.1080 (2)	0.0419 (10)
N6	0.4529 (3)	0.1618 (4)	0.0973 (3)	0.0585 (12)
H6A	0.5053	0.1380	0.1104	0.070*
N7	0.1773 (2)	0.3582 (4)	0.0787 (2)	0.0419 (10)
N8	0.1388 (3)	0.5486 (4)	0.0299 (2)	0.0523 (11)
H8A	0.1310	0.6360	0.0256	0.063*
C1	0.1229 (3)	0.3352 (5)	0.2824 (3)	0.0524 (13)
H1A	0.1689	0.3812	0.3083	0.063*
C2	−0.0017 (3)	0.2583 (5)	0.2543 (3)	0.0514 (13)
C3	0.0469 (3)	0.2151 (5)	0.2013 (3)	0.0444 (12)
H3A	0.0300	0.1582	0.1577	0.053*
C4	−0.0900 (3)	0.2345 (8)	0.2636 (4)	0.088 (2)
H4B	−0.1132	0.1789	0.2216	0.106*
H4C	−0.0951	0.1927	0.3134	0.106*
H4D	−0.1184	0.3170	0.2617	0.106*
C7	0.2908 (3)	0.1021 (5)	0.3148 (3)	0.0505 (13)
H7A	0.2967	0.1846	0.3421	0.061*
C6	0.3138 (3)	−0.0142 (5)	0.3462 (3)	0.0471 (12)
C5	0.2619 (3)	−0.0401 (5)	0.2240 (3)	0.0524 (13)
H5A	0.2434	−0.0811	0.1747	0.063*
C8	0.3533 (4)	−0.0538 (6)	0.4250 (3)	0.0776 (19)
H8B	0.3613	0.0220	0.4585	0.093*
H8C	0.3193	−0.1162	0.4487	0.093*
H8D	0.4054	−0.0931	0.4182	0.093*
C9	0.3944 (3)	0.1653 (6)	0.1452 (3)	0.0594 (15)
H9A	0.4017	0.1430	0.2003	0.071*
C10	0.4210 (3)	0.2005 (5)	0.0239 (3)	0.0489 (13)
C11	0.3417 (3)	0.2255 (5)	0.0322 (3)	0.0464 (12)
H11A	0.3026	0.2560	−0.0095	0.056*
C12	0.4716 (4)	0.2074 (7)	−0.0438 (3)	0.0795 (19)
H12A	0.4379	0.2363	−0.0898	0.095*
H12B	0.5154	0.2690	−0.0319	0.095*
H12C	0.4940	0.1224	−0.0536	0.095*
C13	0.1774 (3)	0.4850 (5)	0.0911 (3)	0.0490 (13)
H13A	0.2025	0.5267	0.1379	0.059*
C14	0.1121 (3)	0.4588 (5)	−0.0261 (3)	0.0502 (13)
C15	0.1363 (3)	0.3410 (5)	0.0054 (3)	0.0486 (13)
H15A	0.1269	0.2582	−0.0210	0.058*
C16	0.0681 (4)	0.4970 (6)	−0.1030 (3)	0.084 (2)
H16A	0.0550	0.4192	−0.1336	0.101*
H16B	0.0185	0.5428	−0.0945	0.101*
H16C	0.1026	0.5531	−0.1308	0.101*
C17	0.2199 (4)	−0.1017 (7)	−0.0275 (4)	0.0677 (17)
C18	0.4214 (5)	0.5436 (9)	0.1974 (4)	0.093 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0440 (3)	0.0405 (3)	0.0431 (3)	0.0074 (3)	0.0050 (2)	0.0094 (3)
S1	0.0602 (8)	0.0303 (6)	0.0415 (7)	0.0044 (6)	0.0029 (6)	0.0007 (6)
S2	0.0487 (8)	0.0476 (8)	0.0570 (8)	−0.0109 (7)	0.0025 (6)	−0.0077 (7)
F1	0.095 (3)	0.193 (5)	0.101 (3)	0.080 (3)	−0.025 (3)	−0.050 (3)
F2	0.093 (3)	0.111 (3)	0.121 (3)	−0.016 (3)	0.049 (3)	−0.023 (3)
F3	0.114 (3)	0.088 (3)	0.085 (3)	0.016 (2)	0.019 (2)	−0.040 (2)
F4	0.178 (5)	0.160 (5)	0.093 (3)	−0.120 (4)	0.045 (3)	−0.013 (3)
F5	0.160 (4)	0.179 (5)	0.058 (2)	−0.083 (4)	0.024 (3)	−0.029 (3)
F6	0.087 (3)	0.207 (6)	0.191 (6)	0.004 (4)	0.063 (4)	−0.035 (5)
O1	0.069 (3)	0.051 (2)	0.062 (2)	0.0045 (19)	0.0016 (19)	−0.0210 (19)
O2	0.073 (3)	0.077 (3)	0.050 (2)	0.013 (2)	−0.0019 (19)	0.012 (2)
O3	0.112 (3)	0.036 (2)	0.089 (3)	0.001 (2)	0.031 (3)	0.013 (2)
O4	0.079 (3)	0.046 (2)	0.105 (3)	−0.015 (2)	0.027 (3)	−0.005 (2)
O5	0.092 (3)	0.051 (3)	0.138 (4)	0.011 (2)	−0.023 (3)	−0.022 (3)
O6	0.062 (3)	0.169 (5)	0.058 (3)	−0.046 (3)	0.005 (2)	−0.020 (3)
N1	0.043 (2)	0.042 (2)	0.043 (2)	0.004 (2)	0.0046 (18)	0.002 (2)
N2	0.070 (3)	0.055 (3)	0.048 (3)	0.015 (2)	0.012 (2)	−0.005 (2)
N3	0.051 (2)	0.036 (2)	0.042 (2)	0.0017 (19)	0.0060 (19)	0.0064 (19)
N4	0.075 (3)	0.029 (2)	0.058 (3)	0.003 (2)	−0.001 (2)	0.008 (2)
N5	0.044 (2)	0.039 (2)	0.043 (2)	0.0029 (19)	0.0031 (19)	0.0060 (19)
N6	0.039 (2)	0.073 (3)	0.064 (3)	0.014 (2)	0.006 (2)	0.009 (3)
N7	0.050 (2)	0.032 (2)	0.043 (2)	0.0050 (19)	−0.0010 (19)	0.0019 (19)
N8	0.069 (3)	0.030 (2)	0.057 (3)	0.004 (2)	−0.002 (2)	0.004 (2)
C1	0.051 (3)	0.049 (3)	0.057 (3)	0.000 (3)	0.003 (3)	−0.003 (3)
C2	0.048 (3)	0.059 (3)	0.047 (3)	0.003 (3)	0.001 (2)	0.004 (3)
C3	0.045 (3)	0.046 (3)	0.041 (3)	0.001 (2)	−0.002 (2)	0.000 (2)
C4	0.050 (3)	0.145 (7)	0.071 (4)	0.001 (4)	0.019 (3)	0.006 (5)
C7	0.078 (4)	0.031 (3)	0.041 (3)	0.002 (3)	0.003 (3)	−0.002 (2)
C6	0.059 (3)	0.036 (3)	0.045 (3)	0.000 (2)	0.002 (3)	0.008 (2)
C5	0.067 (4)	0.042 (3)	0.048 (3)	−0.003 (3)	−0.001 (3)	0.000 (3)
C8	0.107 (5)	0.058 (4)	0.063 (4)	0.004 (4)	−0.014 (4)	0.016 (3)
C9	0.044 (3)	0.084 (4)	0.050 (3)	0.011 (3)	0.004 (3)	0.015 (3)
C10	0.053 (3)	0.041 (3)	0.053 (3)	0.000 (2)	0.009 (3)	0.000 (2)
C11	0.047 (3)	0.047 (3)	0.045 (3)	0.003 (3)	0.003 (2)	0.008 (3)
C12	0.074 (4)	0.102 (5)	0.066 (4)	−0.001 (4)	0.022 (3)	−0.001 (4)
C13	0.060 (3)	0.039 (3)	0.046 (3)	0.004 (3)	−0.004 (3)	−0.002 (2)
C14	0.064 (3)	0.035 (3)	0.049 (3)	0.004 (3)	−0.004 (3)	0.004 (2)
C15	0.067 (4)	0.031 (3)	0.045 (3)	0.004 (2)	−0.006 (3)	−0.003 (2)
C16	0.120 (6)	0.064 (4)	0.062 (4)	0.019 (4)	−0.026 (4)	0.004 (3)
C17	0.070 (4)	0.066 (4)	0.067 (4)	0.006 (3)	0.007 (3)	−0.015 (3)
C18	0.091 (6)	0.111 (6)	0.082 (5)	−0.045 (5)	0.029 (4)	−0.025 (5)

Geometric parameters (Å, º)

Cu1—N1	1.992 (4)	N6—H6A	0.9000
Cu1—N5	1.994 (4)	N7—C13	1.307 (6)
Cu1—N7	2.000 (4)	N7—C15	1.369 (6)
Cu1—N3	2.001 (4)	N8—C13	1.333 (6)
Cu1—O1	2.639 (3)	N8—C14	1.362 (6)
Cu1—O4	2.867 (4)	N8—H8A	0.9000
S1—O2	1.429 (4)	C1—H1A	0.9601
S1—O3	1.430 (4)	C2—C3	1.334 (7)
S1—O1	1.433 (3)	C2—C4	1.491 (7)
S1—C17	1.815 (6)	C3—H3A	0.9600
S2—O6	1.412 (4)	C4—H4B	0.9599
S2—O4	1.417 (4)	C4—H4C	0.9600
S2—O5	1.424 (4)	C4—H4D	0.9600
S2—C18	1.800 (7)	C7—C6	1.337 (6)
F1—C17	1.302 (7)	C7—H7A	0.9600
F2—C17	1.341 (7)	C6—C8	1.488 (7)
F3—C17	1.323 (6)	C5—H5A	0.9600
F4—C18	1.294 (8)	C8—H8B	0.9600
F5—C18	1.303 (8)	C8—H8C	0.9600
F6—C18	1.348 (10)	C8—H8D	0.9601
N1—C1	1.309 (6)	C9—H9A	0.9599
N1—C3	1.379 (6)	C10—C11	1.346 (6)
N2—C1	1.345 (6)	C10—C12	1.485 (7)
N2—C2	1.371 (6)	C11—H11A	0.9601
N2—H2A	0.9001	C12—H12A	0.9599
N3—C5	1.319 (6)	C12—H12B	0.9599
N3—C7	1.378 (6)	C12—H12C	0.9600
N4—C5	1.329 (6)	C13—H13A	0.9600
N4—C6	1.359 (6)	C14—C15	1.357 (6)
N4—H4A	0.9000	C14—C16	1.484 (7)
N5—C9	1.312 (6)	C15—H15A	0.9600
N5—C11	1.366 (6)	C16—H16A	0.9600
N6—C9	1.317 (6)	C16—H16B	0.9600
N6—C10	1.365 (6)	C16—H16C	0.9600
N1—Cu1—N5	172.42 (16)	C2—C4—H4C	109.5
N1—Cu1—N7	88.55 (16)	H4B—C4—H4C	109.5
N5—Cu1—N7	92.67 (16)	C2—C4—H4D	109.2
N1—Cu1—N3	89.41 (16)	H4B—C4—H4D	109.5
N5—Cu1—N3	89.70 (15)	H4C—C4—H4D	109.5
N7—Cu1—N3	176.70 (16)	C6—C7—N3	110.6 (4)
N1—Cu1—O1	95.62 (14)	C6—C7—H7A	124.6
N5—Cu1—O1	91.89 (14)	N3—C7—H7A	124.7
N7—Cu1—O1	88.63 (14)	C7—C6—N4	105.1 (4)
N3—Cu1—O1	89.00 (14)	C7—C6—C8	132.9 (5)
N1—Cu1—O4	88.29 (14)	N4—C6—C8	121.9 (5)
N5—Cu1—O4	84.14 (14)	N3—C5—N4	110.6 (5)
N7—Cu1—O4	97.01 (14)	N3—C5—H5A	124.4
N3—Cu1—O4	85.50 (14)	N4—C5—H5A	125.0
O1—Cu1—O4	173.23 (12)	C6—C8—H8B	110.0
O2—S1—O3	115.3 (3)	C6—C8—H8C	109.8
O2—S1—O1	115.5 (2)	H8B—C8—H8C	109.5
O3—S1—O1	114.3 (2)	C6—C8—H8D	108.7
O2—S1—C17	102.8 (3)	H8B—C8—H8D	109.5
O3—S1—C17	102.8 (3)	H8C—C8—H8D	109.5
O1—S1—C17	103.7 (3)	N5—C9—N6	111.3 (5)
O6—S2—O4	118.5 (3)	N5—C9—H9A	124.1
O6—S2—O5	111.6 (3)	N6—C9—H9A	124.6
O4—S2—O5	112.3 (3)	C11—C10—N6	104.4 (4)
O6—S2—C18	103.7 (3)	C11—C10—C12	133.6 (5)
O4—S2—C18	105.3 (3)	N6—C10—C12	122.0 (5)
O5—S2—C18	103.6 (4)	C10—C11—N5	110.8 (4)
S1—O1—Cu1	166.5 (2)	C10—C11—H11A	124.5
S2—O4—Cu1	144.1 (3)	N5—C11—H11A	124.7
C1—N1—C3	106.1 (4)	C10—C12—H12A	109.1
C1—N1—Cu1	128.4 (3)	C10—C12—H12B	109.2
C3—N1—Cu1	125.5 (3)	H12A—C12—H12B	109.5
C1—N2—C2	107.9 (4)	C10—C12—H12C	110.1
C1—N2—H2A	126.4	H12A—C12—H12C	109.5
C2—N2—H2A	125.8	H12B—C12—H12C	109.5
C5—N3—C7	104.8 (4)	N7—C13—N8	111.1 (4)
C5—N3—Cu1	125.9 (3)	N7—C13—H13A	124.3
C7—N3—Cu1	129.1 (3)	N8—C13—H13A	124.6
C5—N4—C6	108.9 (4)	C15—C14—N8	104.7 (4)
C5—N4—H4A	126.0	C15—C14—C16	132.8 (5)
C6—N4—H4A	125.1	N8—C14—C16	122.5 (5)
C9—N5—C11	104.8 (4)	C14—C15—N7	110.3 (4)
C9—N5—Cu1	124.6 (3)	C14—C15—H15A	124.2
C11—N5—Cu1	130.5 (3)	N7—C15—H15A	125.5
C9—N6—C10	108.7 (4)	C14—C16—H16A	109.1
C9—N6—H6A	126.0	C14—C16—H16B	110.0
C10—N6—H6A	125.3	H16A—C16—H16B	109.5
C13—N7—C15	105.4 (4)	C14—C16—H16C	109.3
C13—N7—Cu1	124.3 (3)	H16A—C16—H16C	109.5
C15—N7—Cu1	130.0 (3)	H16B—C16—H16C	109.5
C13—N8—C14	108.5 (4)	F1—C17—F3	107.2 (5)
C13—N8—H8A	126.6	F1—C17—F2	107.9 (6)
C14—N8—H8A	124.9	F3—C17—F2	106.4 (5)
N1—C1—N2	110.2 (5)	F1—C17—S1	113.1 (5)
N1—C1—H1A	124.7	F3—C17—S1	112.1 (5)
N2—C1—H1A	125.0	F2—C17—S1	109.9 (4)
C3—C2—N2	105.8 (5)	F4—C18—F5	110.7 (7)
C3—C2—C4	131.8 (5)	F4—C18—F6	104.6 (7)
N2—C2—C4	122.3 (5)	F5—C18—F6	105.8 (7)
C2—C3—N1	109.9 (4)	F4—C18—S2	112.6 (6)
C2—C3—H3A	125.0	F5—C18—S2	113.3 (5)
N1—C3—H3A	125.1	F6—C18—S2	109.2 (6)
C2—C4—H4B	109.7

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O2^i	0.90	2.16	2.910 (6)	141
N4—H4A···O5^ii	0.90	2.04	2.839 (6)	147
N6—H6A···O6^iii	0.90	1.96	2.840 (6)	167
N8—H8A···O3^iv	0.90	1.99	2.872 (5)	165

Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x, y−1, z; (iii) −x+1, y−1/2, −z+1/2; (iv) x, y+1, z.

(IV) aquatetrakis(2-ethyl-5-methyl-1H-imidazole-κN³)copper(II) trifluoromethanesulfonate

Crystal data

[Cu(C6H10N2)4(H2O)](CF3SO3)2	F(000) = 1700
Mr = 820.34	Dx = 1.419 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 15.408 (3) Å	θ = 8.8–12.5°
b = 12.627 (3) Å	µ = 0.76 mm^−1
c = 20.380 (4) Å	T = 293 K
β = 104.37 (3)°	Prism, blue
V = 3841.0 (14) Å^3	0.25 × 0.15 × 0.12 mm
Z = 4

Data collection

Enraf–Nonius CAD-4 diffractometer	2847 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.034
Graphite monochromator	θmax = 25.0°, θmin = 1.9°
ω scan	h = −18→17
Absorption correction: ψ scan (North et al., 1968)	k = 0→15
Tmin = 0.807, Tmax = 0.913	l = 0→24
6948 measured reflections	3 standard reflections every 7200 min
6740 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.155	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.001P)^2 + 14P] where P = (Fo^2 + 2Fc^2)/3
6740 reflections	(Δ/σ)max = 0.001
460 parameters	Δρmax = 0.43 e Å^−3
2 restraints	Δρmin = −0.34 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.26043 (6)	0.14810 (7)	0.24746 (4)	0.0621 (3)
S1	0.27679 (16)	−0.0416 (2)	−0.12107 (11)	0.0828 (6)
S2	0.78397 (16)	0.0321 (2)	0.40456 (11)	0.0846 (7)
O1W	0.2678 (4)	0.3349 (4)	0.2382 (3)	0.0957 (17)
H1A	0.2875	0.3614	0.2775	0.115*
H1B	0.2157	0.3588	0.2205	0.115*
O1	0.1911 (5)	−0.0326 (7)	−0.1595 (4)	0.172 (4)
O2	0.2839 (7)	−0.0634 (7)	−0.0544 (3)	0.210 (5)
O3	0.3293 (6)	0.0387 (7)	−0.1367 (5)	0.186 (4)
O4	0.7787 (6)	0.0795 (7)	0.4635 (3)	0.171 (4)
O5	0.7124 (4)	0.0443 (9)	0.3492 (3)	0.188 (4)
O6	0.8065 (7)	−0.0747 (7)	0.4119 (6)	0.208 (4)
F1	0.2659 (9)	−0.2300 (8)	−0.1550 (8)	0.309 (8)
F2	0.3345 (8)	−0.1443 (8)	−0.2092 (5)	0.262 (5)
F3	0.3914 (7)	−0.1903 (10)	−0.1187 (6)	0.280 (7)
F4	0.8866 (5)	0.0517 (9)	0.3263 (4)	0.230 (5)
F5	0.8633 (11)	0.1902 (8)	0.3724 (8)	0.313 (9)
F6	0.9475 (6)	0.0782 (11)	0.4229 (5)	0.273 (6)
N1	0.3922 (4)	0.1471 (5)	0.2960 (3)	0.0661 (16)
N2	0.5363 (4)	0.1265 (6)	0.3337 (3)	0.078 (2)
H2A	0.5918	0.0996	0.3398	0.094*
N3	0.2288 (3)	0.1529 (5)	0.3368 (3)	0.0602 (15)
N4	0.2061 (4)	0.1216 (6)	0.4359 (3)	0.080 (2)
H4A	0.2071	0.0880	0.4750	0.096*
N5	0.1292 (4)	0.1455 (5)	0.2007 (3)	0.0648 (16)
N6	−0.0154 (4)	0.1234 (6)	0.1706 (3)	0.0761 (19)
H6A	−0.0697	0.0956	0.1688	0.091*
N7	0.2892 (4)	0.1268 (5)	0.1579 (3)	0.0641 (17)
N8	0.3050 (4)	0.0678 (6)	0.0617 (3)	0.079 (2)
H8A	0.2991	0.0260	0.0252	0.095*
C1	0.4616 (5)	0.0890 (7)	0.2906 (4)	0.070 (2)
C2	0.5142 (5)	0.2124 (7)	0.3672 (4)	0.071 (2)
C3	0.4251 (5)	0.2250 (6)	0.3440 (3)	0.066 (2)
H3A	0.3903	0.2792	0.3585	0.079*
C4	0.4618 (7)	−0.0068 (7)	0.2479 (4)	0.094 (3)
H4B	0.4263	0.0100	0.2028	0.113*	0.55
H4C	0.5229	−0.0170	0.2444	0.113*	0.55
C5	0.432 (2)	−0.105 (2)	0.2657 (12)	0.175 (15)	0.55
H5A	0.4345	−0.1561	0.2317	0.263*	0.55
H5B	0.3709	−0.0977	0.2692	0.263*	0.55
H5C	0.4689	−0.1269	0.3085	0.263*	0.55
H4D	0.4006	−0.0254	0.2254	0.113*	0.45
H4E	0.4931	0.0092	0.2133	0.113*	0.45
C5'	0.5036 (19)	−0.094 (3)	0.2867 (15)	0.149 (16)	0.45
H5'1	0.5050	−0.1531	0.2573	0.224*	0.45
H5'2	0.4705	−0.1132	0.3191	0.224*	0.45
H5'3	0.5637	−0.0753	0.3100	0.224*	0.45
C6	0.5829 (5)	0.2753 (7)	0.4166 (4)	0.103 (3)
H6B	0.5533	0.3325	0.4332	0.124*
H6C	0.6108	0.2297	0.4535	0.124*
H6D	0.6277	0.3033	0.3960	0.124*
C7	0.2434 (5)	0.0859 (7)	0.3873 (3)	0.064 (2)
C8	0.1643 (5)	0.2145 (8)	0.4161 (4)	0.075 (2)
C9	0.1784 (5)	0.2344 (7)	0.3549 (4)	0.073 (2)
H9A	0.1575	0.2957	0.3277	0.088*
C10	0.2943 (5)	−0.0149 (6)	0.3937 (4)	0.081 (2)
H10A	0.3037	−0.0321	0.3501	0.097*
H10B	0.2588	−0.0702	0.4062	0.097*
C11	0.3848 (5)	−0.0123 (7)	0.4449 (4)	0.102 (3)
H11A	0.4147	−0.0793	0.4466	0.123*
H11B	0.4209	0.0421	0.4321	0.123*
H11C	0.3755	0.0036	0.4888	0.123*
C12	0.1174 (5)	0.2776 (8)	0.4588 (4)	0.107 (3)
H12A	0.0932	0.3409	0.4351	0.128*
H12B	0.0697	0.2366	0.4687	0.128*
H12C	0.1596	0.2962	0.5003	0.128*
C13	0.0636 (5)	0.0883 (7)	0.2113 (3)	0.067 (2)
C14	0.0020 (6)	0.2068 (7)	0.1329 (4)	0.076 (2)
C15	0.0913 (5)	0.2207 (7)	0.1512 (4)	0.072 (2)
H15A	0.1236	0.2733	0.1329	0.086*
C16	0.0692 (6)	−0.0025 (7)	0.2570 (4)	0.091 (3)
H16A	0.0464	0.0191	0.2947	0.109*
H16B	0.1313	−0.0200	0.2743	0.109*
C17	0.0202 (8)	−0.0965 (9)	0.2299 (5)	0.169 (6)
H17A	0.0279	−0.1512	0.2635	0.203*
H17B	−0.0424	−0.0806	0.2135	0.203*
H17C	0.0436	−0.1201	0.1929	0.203*
C18	−0.0706 (5)	0.2664 (8)	0.0839 (4)	0.111 (3)
H18A	−0.1285	0.2369	0.0826	0.133*
H18B	−0.0691	0.3392	0.0976	0.133*
H18C	−0.0594	0.2618	0.0397	0.133*
C19	0.2669 (4)	0.0503 (7)	0.1126 (3)	0.066 (2)
C20	0.3527 (5)	0.1597 (8)	0.0732 (4)	0.077 (2)
C21	0.3440 (5)	0.1956 (7)	0.1337 (4)	0.077 (2)
H21A	0.3707	0.2592	0.1555	0.092*
C22	0.2097 (5)	−0.0440 (7)	0.1152 (4)	0.086 (2)
H22A	0.1987	−0.0479	0.1595	0.103*
H22B	0.2405	−0.1073	0.1080	0.103*
C23	0.1206 (6)	−0.0405 (8)	0.0635 (4)	0.121 (4)
H23A	0.0847	−0.1016	0.0666	0.145*
H23B	0.0894	0.0223	0.0711	0.145*
H23C	0.1316	−0.0376	0.0192	0.145*
C24	0.4028 (6)	0.2048 (9)	0.0256 (4)	0.128 (4)
H24A	0.3961	0.1589	−0.0128	0.154*
H24B	0.3795	0.2736	0.0108	0.154*
H24C	0.4652	0.2107	0.0483	0.154*
C25	0.3195 (8)	−0.1534 (10)	−0.1521 (6)	0.152 (5)
C26	0.8761 (9)	0.0930 (15)	0.3802 (7)	0.143 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0600 (5)	0.0766 (6)	0.0480 (4)	0.0012 (5)	0.0105 (4)	0.0009 (5)
S1	0.0920 (16)	0.0810 (17)	0.0703 (13)	0.0012 (14)	0.0107 (12)	0.0008 (13)
S2	0.0802 (15)	0.106 (2)	0.0650 (13)	0.0062 (14)	0.0140 (11)	−0.0025 (14)
O1W	0.114 (4)	0.085 (4)	0.075 (3)	0.005 (4)	−0.002 (3)	0.003 (3)
O1	0.086 (5)	0.206 (9)	0.205 (8)	0.020 (6)	0.000 (5)	−0.005 (7)
O2	0.398 (14)	0.172 (8)	0.063 (4)	0.069 (9)	0.064 (6)	−0.001 (5)
O3	0.202 (9)	0.113 (7)	0.250 (10)	−0.055 (6)	0.069 (8)	0.028 (7)
O4	0.218 (8)	0.214 (9)	0.099 (5)	−0.046 (7)	0.075 (6)	−0.060 (6)
O5	0.076 (4)	0.382 (14)	0.101 (5)	0.036 (7)	0.011 (4)	0.027 (7)
O6	0.252 (11)	0.110 (7)	0.280 (12)	0.018 (7)	0.098 (9)	0.018 (8)
F1	0.404 (18)	0.110 (7)	0.49 (2)	−0.012 (10)	0.264 (18)	−0.050 (10)
F2	0.408 (15)	0.230 (10)	0.208 (9)	0.122 (10)	0.193 (10)	0.035 (8)
F3	0.243 (11)	0.326 (15)	0.223 (10)	0.195 (11)	−0.035 (8)	0.000 (9)
F4	0.161 (7)	0.397 (15)	0.166 (7)	−0.082 (8)	0.105 (6)	−0.086 (8)
F5	0.47 (2)	0.128 (8)	0.396 (19)	−0.048 (11)	0.217 (17)	0.054 (10)
F6	0.140 (7)	0.46 (2)	0.205 (9)	−0.118 (10)	0.012 (6)	−0.069 (11)
N1	0.063 (4)	0.074 (4)	0.059 (3)	0.000 (4)	0.011 (3)	−0.005 (4)
N2	0.057 (4)	0.103 (6)	0.071 (4)	0.005 (4)	0.009 (3)	−0.001 (4)
N3	0.055 (3)	0.072 (4)	0.052 (3)	0.002 (3)	0.011 (3)	0.001 (3)
N4	0.077 (4)	0.117 (7)	0.047 (4)	−0.005 (4)	0.017 (3)	0.004 (4)
N5	0.061 (3)	0.078 (5)	0.055 (3)	−0.003 (4)	0.015 (3)	0.004 (4)
N6	0.058 (4)	0.098 (6)	0.072 (4)	−0.001 (4)	0.014 (3)	−0.001 (4)
N7	0.062 (4)	0.079 (5)	0.052 (3)	−0.009 (3)	0.013 (3)	−0.006 (3)
N8	0.074 (4)	0.112 (6)	0.051 (4)	−0.004 (4)	0.016 (3)	−0.011 (4)
C1	0.076 (5)	0.074 (6)	0.058 (5)	0.007 (5)	0.012 (4)	−0.005 (4)
C2	0.075 (5)	0.081 (6)	0.061 (5)	−0.011 (5)	0.021 (4)	−0.001 (5)
C3	0.070 (5)	0.072 (6)	0.051 (4)	0.009 (4)	0.007 (4)	−0.001 (4)
C4	0.108 (7)	0.084 (7)	0.079 (6)	0.024 (6)	0.002 (5)	−0.006 (5)
C5	0.36 (5)	0.090 (18)	0.12 (2)	−0.04 (3)	0.14 (3)	−0.019 (17)
C4	0.108 (7)	0.084 (7)	0.079 (6)	0.024 (6)	0.002 (5)	−0.006 (5)
C5'	0.17 (3)	0.10 (2)	0.13 (2)	0.07 (2)	−0.05 (2)	−0.053 (18)
C6	0.088 (6)	0.108 (8)	0.106 (7)	−0.026 (6)	0.011 (5)	−0.022 (6)
C7	0.061 (4)	0.081 (6)	0.048 (4)	−0.004 (4)	0.008 (4)	0.002 (4)
C8	0.063 (5)	0.102 (7)	0.060 (5)	0.001 (5)	0.012 (4)	−0.013 (5)
C9	0.066 (5)	0.088 (6)	0.062 (5)	0.011 (5)	0.010 (4)	−0.001 (4)
C10	0.092 (6)	0.072 (6)	0.079 (5)	0.009 (5)	0.022 (5)	0.020 (5)
C11	0.090 (6)	0.115 (8)	0.094 (6)	0.025 (6)	0.005 (5)	0.023 (6)
C12	0.082 (6)	0.152 (9)	0.092 (6)	0.008 (6)	0.031 (5)	−0.038 (6)
C13	0.062 (5)	0.083 (6)	0.054 (4)	0.006 (5)	0.011 (4)	−0.001 (4)
C14	0.079 (6)	0.092 (7)	0.052 (5)	0.011 (5)	0.005 (4)	−0.003 (5)
C15	0.075 (5)	0.080 (6)	0.058 (5)	0.005 (5)	0.013 (4)	0.010 (4)
C16	0.098 (6)	0.106 (8)	0.062 (5)	−0.035 (6)	0.006 (5)	0.009 (5)
C17	0.226 (14)	0.149 (12)	0.116 (9)	−0.064 (11)	0.011 (9)	0.033 (9)
C18	0.102 (7)	0.136 (9)	0.077 (6)	0.032 (7)	−0.014 (5)	0.015 (6)
C19	0.055 (4)	0.096 (7)	0.050 (4)	0.008 (4)	0.015 (3)	0.003 (4)
C20	0.060 (5)	0.116 (8)	0.054 (4)	−0.002 (5)	0.012 (4)	0.012 (5)
C21	0.068 (5)	0.092 (7)	0.072 (5)	−0.018 (5)	0.019 (4)	−0.002 (5)
C22	0.088 (6)	0.075 (6)	0.097 (6)	−0.005 (5)	0.029 (5)	−0.011 (5)
C23	0.115 (8)	0.136 (9)	0.108 (7)	−0.053 (7)	0.020 (6)	−0.020 (7)
C24	0.111 (7)	0.197 (12)	0.082 (6)	−0.020 (8)	0.035 (6)	0.031 (7)
C25	0.238 (17)	0.131 (12)	0.093 (8)	0.031 (13)	0.052 (10)	0.039 (9)
C26	0.096 (8)	0.239 (18)	0.088 (8)	0.009 (11)	0.013 (7)	−0.010 (10)

Geometric parameters (Å, º)

Cu1—N3	1.999 (5)	C5—H5B	0.9600
Cu1—N7	2.000 (5)	C5—H5C	0.9600
Cu1—N5	2.010 (6)	C4—C5'	1.42 (3)
Cu1—N1	2.026 (5)	C4—H4D	0.9700
Cu1—O1W	2.372 (5)	C4—H4E	0.9700
S1—O1	1.362 (7)	C5'—H5'1	0.9600
S1—O2	1.364 (7)	C5'—H5'2	0.9600
S1—O3	1.383 (7)	C5'—H5'3	0.9600
S1—C25	1.742 (13)	C6—H6B	0.9600
S2—O4	1.364 (6)	C6—H6C	0.9601
S2—O5	1.376 (6)	C6—H6D	0.9600
S2—O6	1.391 (9)	C7—C10	1.483 (10)
S2—C26	1.789 (14)	C8—C9	1.340 (9)
O1W—H1A	0.8499	C8—C12	1.493 (10)
O1W—H1B	0.8500	C9—H9A	0.9600
F1—C25	1.264 (9)	C10—C11	1.521 (9)
F2—C25	1.246 (12)	C10—H10A	0.9600
F3—C25	1.239 (8)	C10—H10B	0.9599
F4—C26	1.262 (14)	C11—H11A	0.9600
F5—C26	1.248 (18)	C11—H11B	0.9601
F6—C26	1.235 (13)	C11—H11C	0.9599
N1—C1	1.323 (9)	C12—H12A	0.9600
N1—C3	1.391 (9)	C12—H12B	0.9600
N2—C1	1.348 (9)	C12—H12C	0.9601
N2—C2	1.368 (9)	C13—C16	1.467 (10)
N2—H2A	0.9000	C14—C15	1.345 (10)
N3—C7	1.309 (8)	C14—C18	1.504 (10)
N3—C9	1.394 (9)	C15—H15A	0.9600
N4—C7	1.340 (8)	C16—C17	1.441 (11)
N4—C8	1.351 (10)	C16—H16A	0.9600
N4—H4A	0.8999	C16—H16B	0.9599
N5—C13	1.304 (9)	C17—H17A	0.9600
N5—C15	1.402 (9)	C17—H17B	0.9600
N6—C13	1.365 (8)	C17—H17C	0.9600
N6—C14	1.369 (9)	C18—H18A	0.9600
N6—H6A	0.9000	C18—H18B	0.9600
N7—C19	1.322 (9)	C18—H18C	0.9601
N7—C21	1.385 (9)	C19—C22	1.490 (10)
N8—C19	1.329 (8)	C20—C21	1.351 (9)
N8—C20	1.363 (10)	C20—C24	1.494 (10)
N8—H8A	0.9000	C21—H21A	0.9600
C1—C4	1.492 (10)	C22—C23	1.510 (10)
C1—C4	1.492 (10)	C22—H22A	0.9600
C2—C3	1.346 (9)	C22—H22B	0.9600
C2—C6	1.495 (10)	C23—H23A	0.9600
C3—H3A	0.9601	C23—H23B	0.9600
C4—C5	1.40 (2)	C23—H23C	0.9600
C4—H4B	0.9700	C24—H24A	0.9600
C4—H4C	0.9700	C24—H24B	0.9600
C5—H5A	0.9600	C24—H24C	0.9599
N3—Cu1—N7	173.9 (3)	N3—C7—C10	127.4 (7)
N3—Cu1—N5	89.4 (2)	N4—C7—C10	122.5 (7)
N7—Cu1—N5	89.4 (2)	C9—C8—N4	105.4 (7)
N3—Cu1—N1	89.8 (2)	C9—C8—C12	131.0 (9)
N7—Cu1—N1	91.3 (2)	N4—C8—C12	123.6 (8)
N5—Cu1—N1	178.5 (3)	C8—C9—N3	109.8 (7)
N3—Cu1—O1W	94.0 (2)	C8—C9—H9A	125.5
N7—Cu1—O1W	92.0 (2)	N3—C9—H9A	124.8
N5—Cu1—O1W	92.3 (2)	C7—C10—C11	114.6 (7)
N1—Cu1—O1W	89.0 (2)	C7—C10—H10A	108.2
O1—S1—O2	114.6 (6)	C11—C10—H10A	108.5
O1—S1—O3	110.3 (6)	C7—C10—H10B	108.9
O2—S1—O3	118.1 (6)	C11—C10—H10B	108.6
O1—S1—C25	105.0 (6)	H10A—C10—H10B	107.9
O2—S1—C25	104.7 (5)	C10—C11—H11A	110.9
O3—S1—C25	102.4 (6)	C10—C11—H11B	108.8
O4—S2—O5	117.6 (5)	H11A—C11—H11B	109.5
O4—S2—O6	113.5 (6)	C10—C11—H11C	108.7
O5—S2—O6	108.9 (7)	H11A—C11—H11C	109.5
O4—S2—C26	106.3 (6)	H11B—C11—H11C	109.5
O5—S2—C26	104.7 (6)	C8—C12—H12A	109.6
O6—S2—C26	104.6 (7)	C8—C12—H12B	109.9
Cu1—O1W—H1A	109.2	H12A—C12—H12B	109.5
Cu1—O1W—H1B	109.1	C8—C12—H12C	108.9
H1A—O1W—H1B	109.9	H12A—C12—H12C	109.5
C1—N1—C3	106.8 (6)	H12B—C12—H12C	109.5
C1—N1—Cu1	134.1 (5)	N5—C13—N6	109.3 (7)
C3—N1—Cu1	119.0 (5)	N5—C13—C16	127.8 (7)
C1—N2—C2	109.0 (6)	N6—C13—C16	122.9 (7)
C1—N2—H2A	125.8	C15—C14—N6	105.9 (7)
C2—N2—H2A	125.2	C15—C14—C18	131.3 (9)
C7—N3—C9	105.4 (6)	N6—C14—C18	122.7 (8)
C7—N3—Cu1	131.6 (5)	C14—C15—N5	109.0 (7)
C9—N3—Cu1	122.8 (5)	C14—C15—H15A	125.1
C7—N4—C8	109.3 (7)	N5—C15—H15A	125.8
C7—N4—H4A	125.5	C17—C16—C13	117.2 (7)
C8—N4—H4A	125.2	C17—C16—H16A	106.3
C13—N5—C15	107.0 (6)	C13—C16—H16A	108.0
C13—N5—Cu1	131.3 (5)	C17—C16—H16B	109.4
C15—N5—Cu1	121.4 (5)	C13—C16—H16B	108.0
C13—N6—C14	108.7 (6)	H16A—C16—H16B	107.6
C13—N6—H6A	125.3	C16—C17—H17A	111.0
C14—N6—H6A	125.9	C16—C17—H17B	110.3
C19—N7—C21	106.5 (6)	H17A—C17—H17B	109.5
C19—N7—Cu1	131.1 (5)	C16—C17—H17C	107.1
C21—N7—Cu1	122.3 (5)	H17A—C17—H17C	109.5
C19—N8—C20	109.4 (7)	H17B—C17—H17C	109.5
C19—N8—H8A	125.0	C14—C18—H18A	110.9
C20—N8—H8A	125.5	C14—C18—H18B	109.1
N1—C1—N2	109.2 (7)	H18A—C18—H18B	109.5
N1—C1—C4	128.1 (8)	C14—C18—H18C	108.4
N2—C1—C4	122.7 (8)	H18A—C18—H18C	109.5
N1—C1—C4	128.1 (8)	H18B—C18—H18C	109.5
N2—C1—C4	122.7 (8)	N7—C19—N8	109.5 (7)
C4—C1—C4	0.0 (11)	N7—C19—C22	127.7 (7)
C3—C2—N2	106.1 (7)	N8—C19—C22	122.7 (8)
C3—C2—C6	131.6 (8)	C21—C20—N8	105.7 (7)
N2—C2—C6	122.3 (7)	C21—C20—C24	130.5 (9)
C2—C3—N1	109.0 (7)	N8—C20—C24	123.9 (8)
C2—C3—H3A	125.1	C20—C21—N7	108.8 (7)
N1—C3—H3A	125.9	C20—C21—H21A	125.1
C5—C4—C1	121.0 (12)	N7—C21—H21A	126.1
C5—C4—H4B	107.1	C19—C22—C23	113.3 (8)
C1—C4—H4B	107.1	C19—C22—H22A	108.6
C5—C4—H4C	107.1	C23—C22—H22A	108.4
C1—C4—H4C	107.1	C19—C22—H22B	109.9
H4B—C4—H4C	106.8	C23—C22—H22B	108.4
C4—C5—H5A	109.5	H22A—C22—H22B	108.1
C4—C5—H5B	109.5	C22—C23—H23A	111.6
H5A—C5—H5B	109.5	C22—C23—H23B	108.4
C4—C5—H5C	109.5	H23A—C23—H23B	109.5
H5A—C5—H5C	109.5	C22—C23—H23C	108.4
H5B—C5—H5C	109.5	H23A—C23—H23C	109.5
C5'—C4—C1	111.9 (13)	H23B—C23—H23C	109.5
C5'—C4—H4D	109.2	C20—C24—H24A	109.3
C1—C4—H4D	109.2	C20—C24—H24B	109.7
C5'—C4—H4E	109.2	H24A—C24—H24B	109.5
C1—C4—H4E	109.2	C20—C24—H24C	109.5
H4D—C4—H4E	107.9	H24A—C24—H24C	109.5
C4—C5'—H5'1	109.5	H24B—C24—H24C	109.5
C4—C5'—H5'2	109.5	F3—C25—F2	101.5 (12)
H5'1—C5'—H5'2	109.5	F3—C25—F1	102.8 (12)
C4—C5'—H5'3	109.5	F2—C25—F1	107.3 (14)
H5'1—C5'—H5'3	109.5	F3—C25—S1	118.2 (11)
H5'2—C5'—H5'3	109.5	F2—C25—S1	116.0 (9)
C2—C6—H6B	108.6	F1—C25—S1	109.7 (10)
C2—C6—H6C	108.3	F6—C26—F5	108.9 (16)
H6B—C6—H6C	109.5	F6—C26—F4	105.5 (13)
C2—C6—H6D	111.6	F5—C26—F4	110.2 (15)
H6B—C6—H6D	109.5	F6—C26—S2	111.7 (11)
H6C—C6—H6D	109.5	F5—C26—S2	110.2 (12)
N3—C7—N4	110.1 (7)	F4—C26—S2	110.2 (11)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O5	0.90	1.95	2.849 (9)	178
N4—H4A···O6^i	0.90	2.37	3.211 (12)	155
N6—H6A···O1^ii	0.90	2.00	2.897 (10)	177
N8—H8A···O2	0.90	1.94	2.841 (9)	179
O1W—H1A···O3^iii	0.85	2.12	2.957 (10)	167

Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x, −y, −z; (iii) x, −y+1/2, z+1/2.